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| United States Patent |
6,156,909
|
|
Kim
, et al.
|
December 5, 2000
|
Preparation of alkylene carbonate using indium halides and mixtures of
same with lead halides as catalyst
Abstract
The present invention relates to a method for preparing alkylene carbonate
by reacting alkylene oxide with carbon dioxide in the presence of a
catalyst system comprising:
a) at least one selected from the group consisting of PbY.sub.2, InY.sub.3
and their mixture, wherein Y is Cl, Br or I; and
b) at least one alkali metal halide selected from the group consisting of
MCl, MBr and MI, wherein M is alkali metal.
| Inventors:
|
Kim; Hoon Sik (Seoul, KR);
Kim; Jai Jun (Kyunggido, KR);
Lee; Sang Deuk (Seoul, KR);
Park; Kun You (Seoul, KR);
Kim; Hong Gon (Seoul, KR)
|
| Assignee:
|
Korea Institute of Science & Technology (Seoul, KR)
|
| Appl. No.:
|
477829 |
| Filed:
|
January 5, 2000 |
Foreign Application Priority Data
| Current U.S. Class: |
549/230 |
| Intern'l Class: |
C07D 317/36; C07D 317/38 |
| Field of Search: |
549/230
|
References Cited
U.S. Patent Documents
| 5350862 | Sep., 1994 | Wagner et al. | 549/230.
|
| Foreign Patent Documents |
| 45-38534 | Dec., 1970 | JP.
| |
Primary Examiner: Dentz; Bernard
Attorney, Agent or Firm: Arent Fox Kintner Plotkin & Kahn, PLLC
Claims
What is claimed is:
1. A method for preparing alkylene carbonate by reacting alkylene oxide
with carbon dioxide in the presence of a catalyst, characterized in that
the catalyst comprises:
a) at least one indium halide selected from the group consisting of
InCl.sub.3, InBr.sub.3 and InI.sub.3 and their mixture or a mixture of at
least one of the preceding with at least one lead halide selected from the
group consisting of PbCl.sub.2, PbBr.sub.2 and PbI.sub.2 ; and
b) at least one alkali metal halide selected from the group consisting of
MCl, MBr and MI, wherein M is alkali metal.
2. A method according to claim 1, wherein the catalyst comprises:
a) at least one indium halide selected from the group consisting of
InCl.sub.3, InBr.sub.3 and InI.sub.3 ; and
3.b) at least one alkali metal halide selected from the group consisting of
MCl, MBr and MI wherein M is alkali metal.
3. A method according to claim 1, wherein the catalyst comprises:
a) at least one lead halide selected from the group consisting of
PbCl.sub.2, PbBr.sub.2 and PbI.sub.2 ;
b) at least one indium halide selected from the group consisting of
InCl.sub.3, InBr.sub.3 and InI.sub.3 ; and
c) at least one alkali metal halide selected from-the group of MCl, MBr and
MI, wherein M is alkali metal.
4. A method according to claim 1, wherein the alkali metal is Na or K.
5. A method according to claim 1, wherein said at least one indium halide
is selected from InCl.sub.3 and InBr.sub.3.
6. A method according to claim 1, wherein the molar ratio of a)/b) is in
the range of 1:20.about.5:1.
7. A method according to claim 1, wherein the amount of catalysts is in the
range of 0.005.about.3 mol % based on the raw material alkylene oxide.
8. A method according to claim 1, wherein the reaction temperature is in
the range of 80.about.180.degree. C.
9. A method according to claim 1, wherein the reaction pressure is in the
range of 10.about.100 atm.
10. A method according to claim 1, wherein the reaction is carried out
without a solvent.
11. A method according to claim 1, wherein the reaction is carried out with
a solvent.
12. A method according to claim 11, wherein the solvent is the same with
the produced alkylene carbonate.
13. A method according to claim 11, wherein the solvent is ethylene
carbonate or propylene carbonate.
14. A method according to claim 1, wherein the alkylene carbonate produced
has the following formula:
##STR3##
wherein R.sub.1 and R.sub.2 are independently hydrogen or C.sub.1
.about.C.sub.4 alkyl group.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for preparing alkylene carbonate
by reacting alkylene oxide with carbon dioxide. More particularly, the
present invention relates to a method for preparing alkylene carbonate by
reacting alkylene oxide with carbon dioxide in the presence of a catalyst
system comprising
a) PbY.sub.2, InY.sub.3 or their mixture and b) MX (M: alkali metal, X, Y:
halide).
2. Description of the Prior Art
Alkylene carbonates are used in polycarbonate synthesis, as an intermediate
in pharmaceutical processes, an oxyalkylation agent in dyestuff syntheses
and a solvent in textile production processes. Conventionally, alkylene
carbonate has been produced by reacting alkylene oxide with carbon dioxide
in the presence of a catalyst, as shown in scheme 1.
##STR1##
There are substantial literatures in the art with respect to the catalytic
reaction of the alkylene oxide and carbon dioxide. Numerous catalysts have
been proposed including alkali or alkali earth metal halide, ammonium
halide and phosphonium halides.
For example, U.S. Pat. No. 4,881,555, U.S. Pat. No. 4,931,571 and Japanese
Laid-Open Patent No. 7-206846 teaches a process for preparing an alkylene
carbonate that employs a catalyst selected from the group consisting of
organic quaternary ammonium halide, organic quaternary phosphonium halide,
organic sulfonium halides and organic antimony halides. Japanese Laid-Open
Patent No. 9-067365 discloses a method for preparing an alkylene
carbonate, wherein a catalyst comprising an alkali or alkali earth metal
halide is used. Japanese Laid-Open Patent No. 8-059557 also discloses an
alkali halide catalyst.
U.S. Pat. No. 2,773,070 introduces as a catalyst an ion exchange resin
containing quaternary phosphonium halide groups, and U.S. Pat. No.
4,233,221 discloses DOWEX and Amberlite ion exchange resin. It was found
that the anion-exchange resin catalysts lose their catalytic activity over
a period of use.
U.S. Pat. No. 4,665,467 and U.S. Pat. No. 5,283,356 disclose methods for
preparing alkylene carbonate by using a phthalocyanine or a porphyrine
catalyst containing Co, Cr, Fe, Mn, Ni, Ti, V and Zr. In addition, JP
7-206847 discloses a process for preparing alkylene carbonate by using a
rubidium or cesium substituted heteropoly acid catalyst.
In order to provide an attractive process for preparing alkylene carbonate,
the process should achieve high selectivity to alkylene carbonate and
should be economical. However, the processes disclosed in the above
literatures has one or more problems in terms of yield, reaction
condition, cost, etc.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a method of producing
alkylene carbonate with a high yield, in a short reaction time and under
mild reaction conditions. More particularly, the object of the present
invention is to provide a method of producing alkylene carbonate under
milder reaction condition by using a new catalyst system comprising a)
lead halides, indium halides or their mixture and b)alkali metal halides.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a new method of preparing alkylene
carbonate by reacting alkylene oxide with carbon-dioxide, which obviates
above mentioned prior art's problem.
The present invention provides a new method of preparing alkylene carbonate
by reacting alkylene oxide with carbon dioxide in the presence of a
catalyst system comprising a) lead halides, indium halides, or their
mixture and b) alkali metal halides.
The present inventors have found that a catalyst system comprising a) lead
halide, indium halides or their mixture and b) alkali metal halides is
more effective than the conventional catalyst system in preparing alkylene
carbonate of the formula
##STR2##
wherein R.sub.1 and R.sub.2 are independently hydrogen or C.sub.1
.about.C.sub.4 alkyl group.
Lead halides (PbY.sub.2) used in the present invention include PbCl.sub.2,
PbBr.sub.2 and PbI.sub.2, indium halides (InY.sub.3) include InCl.sub.3,
InBr.sub.3 and InI.sub.3, and the alkali metal halides (MX) include NaCl,
NaBr, NaI, KCl, KBr, KI, RbCl, RbBr, RbI, CsCl, CsBr and CsI. Preferable
alkali metal is Na or K.
It is preferable to include at least one Br or I in lead halides, indium
halides and alkali metal halides. In composing a catalyst system expressed
as a[PbY.sub.2 ]/b[MX] and/or a[in Y.sub.3 ]/b[MX], the ratio between a
and b is preferably a:b=1:20.about.5:1, more preferably 1:2.about.1:3.
The amount of catalyst is preferably 0.005-3 mol % of the alkylene oxide.
Since the reaction is not greatly influenced by nitrogen, hydrogen,
hydrocarbons and water typically present in carbon dioxide and alkylene
oxide, it is possible to use commercially available carbon dioxide and
alkylene oxide without a purification step.
Considering the equipment and operating cost, it is preferable to operate a
reaction at a pressure of 10.about.100 atm, and a temperature of
80.about.180.degree. C.
Although the above reaction can be performed in the absence of a solvent,
it is possible to use a solvent to prevent excessive heat production
during the reaction. As a solvent, alkylene carbonate identical with the
one to be produced from the reaction is preferable. Thus, ethylene
carbonate is a preferable solvent when ethylene carbonate is synthesized
from ethylene oxide, and propylene carbonate is preferable when propylene
carbonate is synthesized from propylene oxide. Alkylene carbonate
different from the one to be produced from the reaction can be also used
as a solvent. For example, propylene carbonate can be used as a solvent in
the synthesis of ethylene carbonate (see Examples 56-59).
The reaction could be performed by a batch process using the reactor
provided with a stirrer or by a continuous process using a bubble column.
EXAMPLES
The present invention will be further illustrated by the following
examples, but, of course, should not construed as in any way limiting its
scope.
Example 1
After ethylene oxide (16.80 g, 380 mmol), KI (284 mg, 1.71 mmol) and
InCl.sub.3 (183 mg, 0.83 mmol) were added to a 200 ml high pressure
reactor, the reactor was pressurized to 10 atm with CO.sub.2. The reactor
was heated to 100.degree. C., and then carbon dioxide was injected again
to the pressure of 30 atm. During the reaction, carbon dioxide was
continuously supplied to maintain the pressure of the reactor at 30 atm.
After the reaction at 100.degree. C. for 1 hour, the reactor was cooled to
room temperature. Volatiles were removed and the solid product was
isolated and weighed to be 33.2 g. The yield analyzed by gas-liquid
chromatography was 99%.
The yield was calculated as follows:
##EQU1##
Examples 2.about.15
The process of Example 1 was repeated except that different catalyst
systems comprising PbX.sub.2 and alkali metal halide were employed in
place of catalyst system comprising InI.sub.3 and KI. The results are
shown in Table 1.
TABLE 1
______________________________________
Product
Example Catalyst system weight (g) Yield (%)
______________________________________
2 PbCl.sub.2
NaBr 5.0 15
3 NaI 31.6 94
4 PbBr.sub.2 NaBr 7.1 21
5 NaI 32.6 97
6 PbI.sub.2 NaCl 19.5 58
7 NaBr 23.8 71
8 NaI 33.2 99
9 PbCl.sub.2 KBr 4.0 12
10 KI 32.9 98
11 PbBr.sub.2 KBr 10.1 30
12 KI 32.9 98
13 PbI.sub.2 KCl 22.8 68
14 KBr 26.2 78
15 KI 33.2 99
______________________________________
Examples 16.about.28
The process of Example 1 was repeated except that different catalyst
systems comprising indium halide and alkali metal halide were employed in
place of catalyst system comprising InI.sub.3 and KI. The results are
shown in Table 2.
TABLE 2
______________________________________
Product
Example Catalyst system weight (g) Yield (%)
______________________________________
16 InCl.sub.3
NaBr 4.0 12
17 NaI 32.9 98
18 InBr.sub.3 NaBr 9.4 28
19 NaI 33.2 96
20 InI.sub.3 NaCl 27.9 83
21 NaBr 29.9 89
22 NaI 33.2 99
23 InCl.sub.3 KBr 5.7 17
24 InBr.sub.3 KBr 12.8 38
25 KI 32.9 98
26 InI.sub.3 KCl 31.9 95
27 KBr 32.6 97
28 KI 33.2 99
______________________________________
Examples 29.about.39
The process of Example 1 was repeated except that different catalyst
systems comprising lead or indium halide and alkali metal halide were
employed and the molar ratios of lead or indium halide to alkali metal
halide were in the range of 1:20.about.5:1. The results are shown in Table
3.
TABLE 3
______________________________________
Example Catalyst system
a:b Product weight (g)
Yield (%)
______________________________________
29 PbBr.sub.2 :KI
1:5 27.9 83
30 PbBr.sub.2 :KI 1:1 32.2 96
31 PbBr.sub.2 :KI 3:1 26.2 78
32 PbI.sub.2 :KBr 1:10 7.7 23
33 PbI.sub.2 :KBr 1:1 23.8 71
34 PbI.sub.2 :KBr 2:1 26.9 80
35 PbI.sub.2 :KBr 5:1 27.5 82
36 InCl.sub.3 :NaI 1:20 5.4 16
37 InCl.sub.3 :NaI 1:10 17.8 53
38 InCl.sub.3 :NaI 1:5 30.6 91
39 InCl.sub.3 :NaI 1:1 32.9 98
______________________________________
Examples 40.about.43
The process of Example 1 was repeated except that the reaction temperatures
were in the range of 80.about.180.degree. C. The results are shown in
Table 4.
TABLE 4
______________________________________
Reaction
Example Temperature (.degree. C.) Product weight (g) Yield (%)
______________________________________
40 80 29.2 87
41 120 33.2 99
42 150 32.6 97
43 180 31.2 93
______________________________________
Examples 44.about.47
The process of Example 1 was repeated except that the reaction pressures
the range of 10.about.100 atm. The results are shown in Table 5.
TABLE 5
______________________________________
Example Reaction Pressure (atm)
Product weight (g)
Yield (%)
______________________________________
44 10 22.8 68
45 50 33.3 99
46 70 33.2 99
47 100 33.2 99
______________________________________
Examples 48.about.52
The process of Example 1 was repeated except that the molar ratios of a
catalyst mixture to the ethylene oxide were in the range of 0.005.about.3.
The results are shown in Table 6.
TABLE 6
______________________________________
Catalyst mixture/
ethylene oxide
Example (mol %) Product weight (g) Yield (%)
______________________________________
48 0.005 5.7 17
49 0.1 17.1 51
50 0.5 33.2 99
51 1 33.2 99
52 3 33.2 99
______________________________________
Examples 53.about.55
The process of Example 1 was repeated except that the different alkylene
oxides were employed. The results are shown in Table
TABLE 7
______________________________________
Product
Example Reactant/Product weight (g) Yield (%)
______________________________________
53 Propylene oxide/ 32.2 96
Propylene carbonate
54 2-methyl-1,2-epoxypropane/ 27.5 82
1,2-dimethylene carbonate
55 2,3-epoxy butane/ 23.8 71
1,2-dimethylethylene carbonate
______________________________________
Examples 56.about.59
The process of Example 1 was repeated except that the different solvents
and/or the different amounts thereof were employed. The results are shown
in Table 8.
TABLE 8
______________________________________
Solvent/
ethylene Product Yield
Example Solvent oxide (wt %) weight (g) (%)
______________________________________
56 Ethylene carbonate
50 32.9 98
57 Propylene carbonate 100 32.2 96
58 Ethylene carbonate 150 30.6 91
59 Propylene carbonate 200 27.9 83
______________________________________
Examples 60.about.62
The process of Example 1 was repeated except that different catalyst
systems comprising lead halide, indium halide and alkali metal halide were
employed in place of catalyst system comprising InI.sub.3 and KI. The
results are shown in Table
TABLE 9
______________________________________
Product
Yield
Example Catalyst Catalyst ratio weight (g) (%)
______________________________________
60 PbCl.sub.2 /NaI/KBr
2:1:1 33.2 99
61 PbCl.sub.2 /InI.sub.3 /KBr 1:1:2 32.2 96
62 PbCl.sub.2 /InI.sub.3 /NaCl 1:1:2 33.2 99
______________________________________
According to the present invention, alkylene carbonate can be economically
produced from alkylene oxide and carbon dioxide by using the catalyst
system comprising a) lead halides, indium halides or their mixture and b)
alkali metal halides.
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